Abstract

Using 550 previously calculated vibrational energy levels and dipole moments we performed simulations of the HCN→HNC isomerization dynamics induced by sub-one-cycle and few-cycle IR pulses, which we represent as Gaussian pulses with 0.25–2 optical cycles in the pulse width. Starting from vibrationally pre-excited states, isomerization probabilities of up to 50% are obtained for optimized pulses. With decreasing number of optical cycles a strong dependence on the carrier-envelope phase (CEP) emerges. Although the optimized pulse parameters change significantly with the number of optical cycles, the distortion by the Gaussian envelope produces nearly equal fields, with a positive lobe followed by a negative one. The positions and areas of the lobes are also almost unchanged, irrespective of the number of cycles in the half-width. Isomerization proceeds via a pump–dumplike mechanism induced by the sequential lobes. The first lobe prepares a wave packet incorporating many delocalized states above the barrier. It is the motion of this wave packet across the barrier, which determines the timing of the pump and dump lobes. The role of the pulse parameters, and in particular of the CEP, is to produce the correct lobe sequence, size and timing within a continuous pulse.